JP5187812B2 - Supramolecular organization and method for producing the same - Google Patents

Description

  The present invention relates to a supramolecular organization comprising a fullerene derivative and a method for producing the same, and more particularly to a supramolecular organization having a special function and a method for producing the same.

  Nanocarbons typified by fullerenes, carbon nanotubes, and carbon nanohorns are expected to be applied to electronic materials, catalysts, and biomaterials, and are attracting attention.

  In recent years, the present inventors have reported that structures of various dimensions (0-dimensional to 3-dimensional) can be arbitrarily produced using fullerene derivatives as a unit among such nanocarbons (for example, Patent Document 1). reference.).

  According to Patent Document 1, the fullerene derivative is composed of a spherical fullerene moiety, an alkyl chain moiety, and a binding moiety that binds them, and the alkyl chain moiety can maintain flatness. By using the balance between the collective force due to the π-π interaction at the fullerene site and the collective force due to the hydrophobic interaction at the alkyl chain site, it is possible to construct nano-sized structures having various dimensions. It becomes possible.

  However, the structure based on the fullerene derivative described in Patent Document 1 merely discloses the characteristics and applications resulting from the nanocarbon, and further development of characteristics and further applications utilizing the characteristics are desired.

  On the other hand, the lotus leaf is known to have super water repellency and self-cleaning ability due to its fractal surface. Specifically, the water droplets on the lotus leaf have a spherical shape due to the fractal surface (that is, super water repellency) and cannot cover the lotus leaf. As a result, the opportunity for dust to adhere to the surface via water is lost and removed along with water droplets on the surface.

There are many attempts to create a super-water-repellent surface by artificially creating a surface structure that imitates the shape of the lotus leaf (see, for example, Non-Patent Document 1). However, the artificial structure thus obtained has the problem of poor resistance and stability to heat and stress. There are no reports or examples that mimic the surface structure of a lotus leaf using fullerene derivatives.
Japanese Patent Application No. 2005-332390 Barbieri et al., Langmuir 23, 1723-1734 (2007)

  As described above, an object of the present invention is to provide a supramolecular structure having super water repellency, more specifically, an expression of further characteristics in the supramolecular structure in which fullerene derivatives are organized, and a method for producing the same.

Invention 1 is a fullerene structure in which fullerene derivatives having a bilayer structure are organized, and the fullerene derivative comprises a fullerene moiety (A) represented by formula (1) and the fullerene moiety (A). A benzene ring bonded to the benzene ring, and first to third substituents R ₁ , R ₂ and R ₃ bonded to the 3, 4 and 5 positions of the benzene ring,

Here, in the formula (1), X is a hydrogen atom or a methyl group, and each of the first and second substituents R ₁ and R ₂ is an alkyl chain containing at least 20 carbon atoms. And the third substituent R ₃ is either a hydrogen atom or an alkyl chain containing at least 20 carbon atoms, and the first to third substituents R ₁ , R ₂ And the alkyl chain of R ₃ is each selected from the group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ), where n is 20 or more And has a flower- like shape, and the fullerene structure is organized in layers.

Inventions 2, in supramolecular organization of inventions 1, wherein the fullerene is bonded to the fullerene site (A) _{is, C 60, C 70, C} 76 _and, being selected from the group consisting of _{C 84} Supramolecular organization.

Inventions 3 is a manufacturing method of the invention one or two of any of the supramolecular organization, comprising the steps of mixing a fullerene derivative, and a 1,4-dioxane, the fullerene derivative of the formula (1 ), A benzene ring bonded to the fullerene moiety (A), and first to third substituents R ₁ bonded to the 3, 4, and 5 positions of the benzene ring, respectively, R ₂ and R ₃ and

Here, in the formula (1), X is a hydrogen atom or a methyl group, and each of the first and second substituents R ₁ and R ₂ is an alkyl chain containing at least 20 carbon atoms. There, the third substituent R ₃ is a hydrogen atom, or a state, and are any of alkyl chains containing at least 20 carbon atoms, the first to third substituents R _1, R The alkyl chains of ₂ and R ₃ are each selected from the group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ), where n is 20 more integers, steps, a step of heating the mixture obtained by the step of mixing, a step of aging the mixture, depending on the step of the aging The solution containing the precipitate formed is characterized by comprising the step of applying.

Inventions 4, in the method of inventions 3, the fullerene to bind to the fullerene part (A) _{is, C 60, C 70, C} 76, _and, characterized in that it is selected from the group consisting of _{C 84.}

Inventions 5, in any of the methods of the inventions 3 or 4, wherein the step of heating, in the temperature range of 60 ° C. to 70 ° C., and carrying out 1 to 2 hours.

Inventions 6, in any of the methods from inventions 3 5, wherein the step of aging, and performs 12 to 24 hours at room temperature.

  The supramolecular structure according to the present invention comprises a fullerene structure in which fullerene derivatives having a bilayer structure are organized. The fullerene derivative includes an alkyl chain having 20 or more carbon atoms bonded to the 3, 4 position or the 3, 4, 5 position of the benzene ring bonded to the fullerene moiety. Further, in the supramolecular organization according to the present invention, such a fullerene structure is organized in layers. As a result, the supramolecular organization of the present invention has a fractal structure and a high specific surface area, which is preferable for an adsorption carrier of a fuel cell catalyst, for example. Furthermore, since the fractal structure expresses super water repellency, it is expected to be applied not only to a water repellent film but also to a new device using it and having a fullerene function.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, the same number is attached | subjected to the same element and the description is abbreviate | omitted.

  The inventors of the present application, in a supramolecular structure composed of the specific fullerene derivative represented by the formula (1), forms a fractal structure having a bilayer structure and functions as a nanostructure basic skeleton. It has been found that it exhibits water repellency.

First, a specific fullerene derivative for allowing the supramolecular organization to exhibit super water repellency will be described.

The fullerene derivative includes a fullerene moiety (A), a benzene ring bonded to the fullerene moiety (A), and first to third substituents R ₁ , R ₂ bonded to the 3, 4, and 5 positions of the benzene ring, respectively. and a R _3.

The fullerene part (A) includes a fullerene composed of sp ² carbon exhibiting a low surface energy and a nitrogen-containing five-membered ring part. Specifically, the fullerene is selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₄ . These fullerenes are produced industrially and are available. Preferably, the fullerene _{is C 60.} This is because _C60 has extremely high _Ih target properties, is the most stable and inexpensive, and thus is easy to handle and easy to chemically modify.

  The nitrogen-containing five-membered ring portion functions in Formula (1) so as to bind the benzene ring and fullerene, and X is a hydrogen atom or a methyl group.

The first and second substituents R ₁ and R ₂ are alkyl chains consisting of sp ³ carbons. More particularly, each of the first substituent R ₁ and the second substituent R ₂ is an alkyl chain containing at least 20 carbon atoms. When the number of carbon atoms is 19 or less, the supramolecular structure exhibits water repellency but does not reach super water repellency. There is no particular upper limit to the number of carbon atoms that each of the first substituent R ₁ and the second substituent R ₂ has, but the upper limit of the number of carbon atoms is about 22 due to the availability of a sample and cost. .

The third substituent R ₃ is either a hydrogen atom or an alkyl chain containing at least 20 carbon atoms. When the third substituent R ₃ is an alkyl chain containing 19 or less carbon atoms, the supramolecular structure exhibits water repellency but does not exhibit super water repellency. The super water repellency when the _third substituent R ₃ is an alkyl chain is almost the same as the super water repellency when the _third substituent R ₃ is a hydrogen atom.

In addition, exemplary alkyl chains of the first to third substituents R ₁ , R _2, and R ₃ (provided that the third substituent R ₃ is not a hydrogen atom) are each alkyl (C _n H _{2n + 1).} ), Alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ). Here, as described above, n ≧ 20 is satisfied.

  Next, the structure of a supramolecular organization exhibiting super water repellency composed of the above-mentioned fullerene derivatives will be described.

  FIG. 1 schematically shows (A) a bilayer structure, (B) a flower-like fullerene structure, and (C) a layered structure in a supramolecular organization according to the present invention.

  FIG. 1A schematically shows a bilayer structure 100 formed by the fullerene derivative 110 represented by the formula (1). FIG. 1B schematically shows a flower-like fullerene structure 120 in which the bilayer structure 100 is organized. FIG. 1C schematically shows a layered structure 130 in which flower-like fullerene structures 120 are stacked.

More specifically, the bilayer structure 100 includes the first to third substituents R ₁ such that the above-described fullerene derivatives 110 are assembled together by the π-π interaction of the fullerene moiety (A). It has a structure arranged so as to gather together by van der Waals forces of R ₂ and R ₃ . This is due to the balance of π-π interaction and van der Waals force between the fullerene derivatives 110 described above. Further, the inter-film distance D in the bimolecular film structure 100 can be controlled by the length of the alkyl chain of the fullerene derivative 110. Moreover, the bilayer structure 100 is very close to the distance between adjacent fullerenes of about 0.87 nm. Thereby, the rigidity of the supramolecular organization is improved.

  The flower-like fullerene structure 120 is a structure in which the bilayer structure 100 is randomly organized, and has a flower-like or gypsum-like shape. This is obtained by forming the bilayer structure 100 in a self-organized manner under specific conditions (solvent, temperature, etc.) described later. The layered structure 130 is a structure in which a flower-like fullerene structure 120 is laminated on a base material 140, for example. The number of lamination is one or more times and is not particularly limited. The base material 140 is an arbitrary substrate such as a silicon substrate or a glass substrate, and the material and shape are not limited as long as the flower-like fullerene structure 120 can be laminated.

  As described above, the inventors of the present application, in the supramolecular structure composed of the fullerene derivative 110 represented by the formula (1), have the bilayer structure 100 as a nanostructure basic skeleton, thereby achieving super water repellency. Found to show. In the present specification, “the bilayer structure 100 is a nano-structure basic skeleton” means a supramolecular organization constructed with the bilayer structure 100 as a basic unit. The supramolecular structure according to the invention has a bilayer structure 100 as a primary structure, a flower-like fullerene structure (FIG. 1 (B)) of the organized structure as a secondary structure, and a layered structure in which they are laminated (FIG. 1). (C)) has a hierarchical organization structure with a tertiary structure. The hierarchical structure having such a layered structure is, for example, a film and is called a (super water-repellent) textured film.

  The inventors of the present application have found for the first time that the supramolecular organization exhibits a super water repellency by having a hierarchical organization structure composed of the above-mentioned fullerene derivative 110. Such super water repellency appears because a surface having low surface energy and fractal interface morphology is formed by hierarchical self-organization of the fullerene derivative 110. That is, the surface of the supramolecular organization is a fractal surface similar to the surface structure of a lotus leaf, and this is the first report of an artificial system (biomimetic system) that mimics the surface structure of a lotus leaf using a fullerene derivative. Please note that.

  Since the supramolecular organization of the present invention is achieved only by the fullerene derivative 110, it is expected to be an environment-friendly super water-repellent material, and also a new material material that combines the function of fullerene and super water repellency.

  Next, a method for producing a supramolecular organization according to the present invention will be described.

  FIG. 2 is a flow chart for producing a supramolecular organization according to the present invention. Each step will be described.

  Step S210: A fullerene derivative and 1,4-dioxane are mixed. Since the fullerene derivative is the same as the above-mentioned fullerene derivative, it will not be redundantly described. Moreover, the above-mentioned fullerene derivative is manufactured by the manufacturing method described in Japanese Patent Application No. 2005-332390 by the inventors of the present application, for example. 1,4-Dioxane is a poor solvent for the fullerene derivative.

The fullerene derivative is produced as follows. Reacting the binding member represented by formula (a), fullerene, and N-methylglycine represented by formula (b).

Here, R ₁ and R ₂ are each an alkyl substituent, R ₃ is a hydrogen atom or an alkyl substituent, and X is a hydrogen atom or a methyl group.

The alkyl substituents for R ₁ , R ₂ and R ₃ (where R ₃ is not a hydrogen atom) are alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H, respectively). _{2n + 1} ). Here, n is an integer of 20 or more.

The fullerene is selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ and C ₈₆ . The reaction step is more specifically refluxed at a temperature of 110 ° C. in toluene as a solvent for 12 to 24 hours (including 12 hours and 24 hours). The reactant obtained in the reacting step may be cooled and chromatographed using toluene and then toluene / n-hexane (mixed 1: 1) as eluent.

With reference to FIG. 2 again, description will be made following step S210.
Step S220: Heat the mixture. By heating, the fullerene derivative can be uniformly dissolved in 1,4-dioxane. In order to make it melt | dissolve uniformly, a heating is performed in the temperature range of 60 to 70 degreeC for 1 hour-2 hours. Since heating can be performed under mild conditions and in a short time, an expensive apparatus is not required, which is industrially preferable.

  Step S230: Aging the mixture dissolved after heating. As a result, the flower-like fullerene structure 120 described with reference to FIG. In order to sufficiently self-assemble, aging is performed at room temperature (temperature range of 15 ° C. to 30 ° C.) for 12 hours to 24 hours. The self-assembled flower-like fullerene structure 120 can be visually observed as a black-brown precipitate (precipitate). Since the yield at this time is 100%, the yield is good and mass production is possible.

  Step S240: Apply a solution containing the precipitate to the substrate. Thus, a supramolecular structure having a hierarchical structure according to the present invention, that is, a layered structure 130 (FIG. 1C) of the flower-like fullerene structure 120 is obtained. For the application to the substrate, any method such as dripping, dipping or spin coating can be employed. The number of times of application to the substrate is not limited. Depending on the application, it may be performed a plurality of times or once. A base material is arbitrary board | substrates, such as a silicon substrate and a glass substrate, for example, The shape may be plate shape and spherical shape and it is arbitrary if it can apply | coat. As described above, through steps S210 to S240, the supramolecular organization according to the present invention is obtained.

  The supramolecular organization (eg, organized membrane) obtained in this manner is easily dissolved in a good solvent such as chloroform, toluene, or benzene, and can be recovered. In addition, the recovered supramolecular organization can be reused by performing steps S210 to S240 again. Also in this case, since the supramolecular organization is regenerated with a yield of 100%, it is environmentally friendly.

  Since the supramolecular structure according to the present invention has super water repellency, as a matter of course, it is used as a super water repellency material for various members and products that are required to be waterproof, anti-fogging, moisture-proof, anti-icing and snow-resistant. Is available. Furthermore, since the supramolecular structure according to the present invention can be applied to an arbitrary base material, it has chemical resistance, acid / alkali resistance and heat resistance in addition to no limitation in use, so it can be used in any environment. But it can be applied. In addition, the supramolecular structure according to the present invention has the function of fullerene (nanocarbon) as well as the super water repellency, so it can be used as, for example, a high mechanical durability material with super water repellency and an optoelectronic material with super water repellency. Is possible. Furthermore, the supramolecular organization of the present invention may be applied to MEMS / NEMS, microchannels, etc. that require low friction and non-wetting.

  The present invention will now be described in detail using specific examples, but it should be noted that the present invention is not limited to these examples.

Fullerene derivatives 3,4,5C ₂₀ C _{60 represented} by the formula (2) were synthesized based on Japanese Patent Application No. 2005-332390. 6 to 8 mg of the obtained fullerene derivative was dissolved in 4 mL of 1,4-dioxane (step S210 in FIG. 2).

  Next, the mixture was heated to 70 ° C. using a hot plate and held for 2 hours (step S220 in FIG. 2). It was visually confirmed that the fullerene derivative was completely dissolved in 1,4-dioxane. Thereafter, the solution was allowed to cool to room temperature (20 ° C.) and aged for 12 hours (step S230 in FIG. 2). A blackish brown precipitate was visually confirmed at the bottom of the solution. The state of mixing immediately after heating at 70 ° C. and the state of precipitation after aging were photographed. The results are shown in FIG.

  Observation of the precipitate was performed by scanning electron microscope SEM (S-4800, Hitachi), optical microscope (BX51, Olympus) equipped with a digital camera (MP5Mc / OL), and transmission electron microscope TEM (JEM equipped with a cryopump). -4000SFX, JEOL).

  A sample for SEM was prepared by placing the precipitate on a silicon substrate (100) and then coating with platinum using ion sputtering (E-1030, Hitachi). The SEM observation condition was an acceleration voltage of 10 kV.

  For the TEM sample, a 1,4-dioxane solution containing precipitates was dropped onto a carbon-coated copper grid (elastic carbon-coated Cu 200-A mesh, Ouken Shoji), and the excess solution was removed using filter paper. And placed in liquid propane maintained at 100K or lower. The TEM observation conditions were an acceleration voltage of 400 kV and a sample holding temperature of 4K. The results of SEM, optical microscope and TEM are shown in FIGS. 4 to 6 and will be described later.

  In order to confirm that the precipitate has a bilayer structure (100 in FIG. 1A), a structural analysis using a powder X-ray diffractometer (RINT Ultimate III, Rigaku), a differential scanning calorimeter ( DSC6220, SII), differential scanning calorimetry (DSC), and spectrophotometers with temperature control cells (NICOLET NEXUS 670FT-IR and Shimadzu U-3600) and FT-IR spectrum measurement and UV / visible Spectrum measurement was performed. These results are shown in FIGS. 7 and 8 and will be described later.

  Next, the 1,4-dioxane solution containing the precipitate was taken out with a dropper and applied onto the Si substrate (step S240 in FIG. 2). The application was performed by dropping. After application, the Si substrate was naturally dried to remove excess solution. Here, the application was performed only once. The surface of a film (also referred to as a layer) formed after coating was observed using an SEM. The observation results are shown in FIG.

  Water droplets were dropped on the obtained film, and the water repellency was evaluated using a contact angle meter (Drop Master, Kyowa Interface Science). The evaluation environment was an air temperature of 21 ° C. and a humidity of 12%. The results are shown in FIG.

  The heat resistance of the obtained film was examined. After maintaining the film at 100 ° C. for 12 hours and 36 hours in the atmosphere, the surface of the film was observed and the water repellency was evaluated. The result after holding for 12 hours is shown in FIG.

  The chemical resistance of the obtained film was examined. The membrane was immersed in each of general-purpose organic solvents acetone and ethanol for 60 seconds, and then dried under vacuum for 12 hours. Thereafter, the contact angle of water was measured. In addition, the acid resistance and alkali resistance of the film were also examined. The membrane was immersed in an acidic solution having pH = 2 and an alkaline solution having pH = 12, respectively, and then washed with pure water and then with acetone, and dried under vacuum for 12 hours. Thereafter, the contact angle was measured. These results are shown in FIGS. 12 to 15 and will be described later.

Comparative Example 1

In Example 1, it replaces with the fullerene derivative of Formula (2), and it is the same except that the fullerene derivative 3, 4, 5C ₁₆ C ₆₀ of Formula (3) is used, and thus the description is omitted.

In the same manner as in Example 1, surface observation by SEM of the precipitate after aging and structural analysis by X-ray diffraction were performed. The results are shown in FIGS. 16 and 17 and will be described later. Similarly to Example 1, a solution containing a precipitate was applied on a Si substrate to form a film. The water repellency of the film was evaluated. The results are shown in FIG.

Comparative Example 2

  In Example 1, chloroform was used instead of 1,4-dioxane. The fullerene derivative represented by the formula (2) was easily dissolved in chloroform at room temperature. Since chloroform is a good solvent for the fullerene derivative, no precipitate was produced. The solution was applied onto the Si substrate using spin coating (rotation speed 1200 rpm) and dried. The surface structure of the obtained film was observed using an atomic force microscope AFM (SPA400, SII) equipped with a probe stage (SPI4000). Observation was performed in tapping mode. The results are shown in FIG. Subsequently, the water-repellent performance of the obtained film was evaluated. The results are shown in FIG.

In Example 1, it replaces with the fullerene derivative of Formula (2), and it is the same except that the fullerene derivative 3, 4C ₂₀ C ₆₀ of Formula (4) is used.

As in Example 1, surface observation by SEM of the precipitate after aging, structural analysis by X-ray diffraction, DSC, FT-IR, and UV measurement were performed. The results are shown in FIGS. 21 to 23 and 24, respectively, and will be described later. Similarly to Example 1, a solution containing a precipitate was applied on a Si substrate to form a film. The water repellency of the film was evaluated. The results are shown in FIG. 25 and will be described later.

Comparative Example 3

In Example 1, since it is the same except that the fullerene derivative 3, 4C ₁₆ C ₆₀ of the formula (5) is used instead of the fullerene derivative of the formula (2), the description is omitted.

In the same manner as in Example 1, SEM of the precipitate after aging and surface observation with an optical microscope and structural analysis by X-ray diffraction were performed. The results are shown in FIGS. 26 and 27 and will be described later.

The experimental conditions of Examples 1 and 2 and Comparative Examples 1 to 3 are summarized in Table 1.

FIG. 3 is a photograph showing the state of the solution immediately after heating in Example 1 and the state of the solution after aging.
The left of the photograph shows the situation immediately after heating at 70 ° C. It was light brown and transparent, and it was found that the fullerene derivative 3,4,5C ₂₀ C ₆₀ was completely dissolved in 1,4-dioxane. The photo on the right shows the state after aging. The solution was divided into a clear area A and a black-brown area B (precipitate and 1,4-dioxane). Region B was a precipitate, and it was confirmed that self-assembly proceeded by aging.

FIG. 4 shows an SEM image and an optical microscope image of the precipitate in Example 1.
From FIG. 4, it can be seen that the precipitate has a spherical shape with a diameter of several μm, and its surface has a flake shape (flower shape) with wrinkles.

FIG. 5 shows a TEM image of the precipitate in Example 1.
FIG. 5 shows in more detail the end of the flakes seen in FIG. The wrinkled state is clearly shown.

FIG. 6 shows a cryo-TEM image and a Fourier transform pattern of the precipitate in Example 1.
In addition to being able to observe in a solution, cryo-TEM is preferable for observation of further details because the sample is less damaged by electron beam irradiation. From the cryo-TEM image of FIG. 6, the end of the flakes of the precipitate has a nanostructure composed of a multilayer lamellar bilayer. Furthermore, the periodicity of 4.4 nm and 2.2 nm was confirmed from the Fourier transform pattern of FIG. These values correspond to the length of one bilayer film in which the alkyl chains (eicosyloxy groups in Example 1) are engaged with each other and half the length of the bilayer film, respectively. Moreover, the spot-like Fourier transform pattern of FIG. 6 suggests that the bilayer structure has high crystallinity.

  As described above, FIGS. 4 to 6 suggest that the precipitate has a flower-like fullerene structure (secondary structure) in which the bilayer structure (primary structure) is organized.

FIG. 7 shows the XRD pattern of the precipitate in Example 1.
The XRD pattern showed clear peaks of (001) and (002). Further, as a result of detailed examination, periodic peaks of (003), (004), (005), (006), and (007) were confirmed. The surface separation calculated from the (001) peak (D in FIG. 1A) was 4.85 nm. Although this value was slightly larger than the period of 4.4 nm described in FIG. 6, it showed a relatively good agreement. This error is due to the influence of the solvent (1,4-dioxane) used as a sample for TEM observation in FIG. 6 and the environment (under ultrahigh vacuum) at the time of TEM observation. The XRD pattern shows a broad peak in the vicinity of 2θ = 10.2 °, which was found to correspond to the distance (0.87 nm) between adjacent fullerene sites. This suggests that fullerene sites have a strong interaction within the same layer.

  FIG. 8 is a graph showing the temperature dependence of the differential calorific value of the precipitate in Example 1.

  When the temperature was changed from the low temperature side to the high temperature side, endothermic peaks were observed at 56.4 ° C. and 59.1 ° C. When the temperature was changed from the high temperature side to the low temperature side, an exothermic peak was observed at 52.0 ° C. This peak was similar to the phase transition behavior often seen in typical bilayer structures such as biological membranes.

According to FT-IR spectrum (not shown) at room temperature, symmetric stretching peak and asymmetric stretching peak of methylene group, respectively, were observed to 2918cm ^-1 and 2849cm ^-1. These peaks correspond to an all-trans-type alkyl chain (eicosyloxy group in Example 1) having crystallinity. Next, the temperature dependence of the FT-IR spectrum was examined. According to the FT-IR spectrum (not shown) at 70 ° C., the symmetric stretch peak and the asymmetric stretch peak of the methylene group are respectively 2918 cm ⁻¹ due to the change of the alkyl chain from the all-trans type to the Gauche type. from to 2923cm ^-1, and were the peak shifted from 2849cm ^-1 to 2852cm ^-1. This is consistent with the phase transition behavior described with reference to FIG.

  The UV-visible spectrum (not shown) at room temperature showed three peaks with maximum absorption values at 330 nm, 270 nm and 222 nm. These maximum absorption values shift to the longer wavelength side of 22 nm, 15 nm, and 10 nm, respectively, compared with the case where the fullerene derivative represented by the formula (2) is dissolved in n-hexane instead of 1,4-dioxane. I found out. These shifts mean the presence of electronic interactions between fullerene sites. Further, the ultraviolet / visible spectrum (not shown) at 70 ° C. was the same as the ultraviolet / visible spectrum at room temperature. Unlike the structural change in the alkyl chain, it was found that the π-π electron interaction between fullerene sites in the supramolecular organization is inert to heat, that is, retains a very strong interaction.

  As described above, it was confirmed from FIGS. 4 to 8 that the precipitate has a bilayer structure (primary structure).

  FIG. 9 shows an SEM image of the surface of the film on the Si substrate in Example 1.

  From FIG. 9, it can be seen that the arrangement of spherical precipitates is similar to the two-dimensional structure filled with hexagonal crystals in the colloidal crystal material, and the surface has a fractal structure. In this way, the deposit can be easily deposited on the Si substrate and formed into a film (tertiary structure). Moreover, the surface of the film was a fractal surface by maintaining and reflecting the flake shape of the surface of the precipitate.

  FIG. 10 is a diagram illustrating a state of water droplets on the film on the Si substrate in the first embodiment.

  The water droplet on the film maintained a spherical shape, and its contact angle was 152.0 °. From this, it was found that the film obtained in Example 1 had super water repellency (contact angle of 150 ° or more).

  FIG. 11 is a diagram showing the heat resistance of the film on the Si substrate in Example 1.

  FIG. 11 shows the SEM image of the surface after heating the film in the atmosphere at 100 ° C. for 12 hours and the state of water droplets. Compared to FIG. 9, even when heated at 100 ° C. for 12 hours, the surface state did not change. The water droplet on the heated film also maintained a spherical shape, and its contact angle was 152.6 °. Although not shown, the state of the surface after heating at 100 ° C. for 36 hours was not changed from FIG. 9 and FIG. Similarly, the contact angle of water was 152.6 °. From this, it was found that the film obtained in Example 1 has not only super water repellency but also heat resistance.

  FIG. 12 is a diagram showing the chemical resistance of the film on the Si substrate in Example 1.

  FIG. 12 shows the state of water droplets on the film after the film is immersed in acetone. The water droplet on the film maintained a spherical shape as in FIG. 9, and its contact angle was 151.5 °.

  FIG. 13 is another diagram showing the chemical resistance of the film on the Si substrate in Example 1. FIG.

  FIG. 13 shows the state of water droplets on the film after the film is immersed in ethanol. The water droplet on the film maintained a spherical shape as in FIG. 9, and its contact angle was 153.1 °. As described above, from FIG. 12 and FIG. 13, it was found that the film obtained in Example 1 has not only super water repellency but also chemical resistance.

  FIG. 14 is a diagram showing acid resistance of the film on the Si substrate in Example 1.

  FIG. 14 shows the state of water droplets on the membrane after the membrane is immersed in an acidic solution with pH = 2. The water droplet on the film maintained a spherical shape as in FIG. 9, and its contact angle was 152.1 °.

  FIG. 15 is a diagram showing the alkali resistance of the film on the Si substrate in Example 1.

  FIG. 15 shows the state of water droplets on the film after the film (with the Si substrate) is immersed in an alkaline solution with a pH = 12. The water droplet on the film maintained a spherical shape as in FIG. 9, and its contact angle was 151.0 °. 14 and 15 that the film obtained in Example 1 has not only super water repellency but also acid / alkali resistance.

FIG. 16 shows an SEM image of the precipitate in Comparative Example 1.
The precipitate of Comparative Example 1 was also spherical, and its surface was flaky (flowery). However, when compared with FIG. 4 of Example 1, it can be seen that the degree of flakes (soot) is small.

FIG. 17 shows the XRD pattern of the precipitate in Comparative Example 1.
The XRD pattern showed periodic peaks of (001), (002), (003), (004), (005), (006), and (007) as in FIG. 4 of Example 1. The interplanar spacing calculated from the (001) peak (intermembrane distance of the bilayer structure) was 4.12 nm.

FIG. 18 is a diagram showing a state of water droplets on the film on the Si substrate in Comparative Example 1.
The water droplet on the membrane was a slightly deformed sphere, and its contact angle was 127.3 °. From this, the film obtained in Comparative Example 1 did not show super water repellency. From comparison between Example 1 and Comparative Example 1, it is suggested that the carbon of each alkyl chain of the fullerene derivative exhibits super water repellency at 20 or more.

FIG. 19 shows an AFM image of the surface of the film on the Si substrate in Comparative Example 2.
The roughness (roughness) of the film surface was as small as about 5 nm, and it was found that the film surface had a smooth surface structure having no fractal shape.

FIG. 20 is a diagram illustrating a state of a droplet of a film on a quartz substrate in the second comparative example.
The droplets on the film had a greatly deformed elliptical shape, and the contact angle was 103.5 °. From this, the film obtained in Comparative Example 2 did not exhibit super water repellency. From the comparison of Example 1 and Comparative Example 2, 1,4-dioxane is suitable as a solvent used for the fullerene derivative to develop super water repellency, and formation of a fractal surface similar to the surface of a lotus leaf is important. It is suggested that

FIG. 21 shows the SEM image of the precipitate in Example 2.
FIG. 22 shows another SEM image of the precipitate in Example 2.
FIG. 23 shows still another SEM image of the precipitate in Example 2.
From FIG. 21 to FIG. 23, the precipitate of Example 2 also has a spherical shape or a flower shape with a diameter of several μm, as in Example 1, and the surface thereof is a flake shape with wrinkles. I understand.

FIG. 24 shows the XRD pattern of the precipitate in Example 2.
The XRD pattern showed periodic peaks of (001), (002), (003), (004), and (005), as in FIG. 4 of Example 1. The interplanar spacing calculated from the (001) peak (intermembrane distance of the bilayer structure) was 3.9 nm. Moreover, DSC, FT-IR, and UV spectrum showed the same result as Example 1, and confirmed that the deposit of Example 2 had a bilayer structure.

FIG. 25 is a diagram showing a state of water droplets on the film on the Si substrate in Example 2. FIG.
The water droplet on the film maintained a spherical shape, and its contact angle was 150.6 °. From this, it was found that the film obtained in Example 2 has super water repellency. A comparison between Example 1 and Example 2 shows that the third substituent R ₃ in the formula (1) is slightly higher in water repellency than the alkyl chain having 20 or more carbon atoms than hydrogen. It was.

FIG. 26 shows an SEM image and an optical microscope image of the precipitate in Comparative Example 3.
Similarly to Example 2, the precipitate of Comparative Example 3 has a spherical shape with a diameter of several μm, and it can be seen that the surface has a flake shape (flower shape) with wrinkles. However, when compared with FIGS. 21 to 23 of Example 2, it can be seen that the degree of flakes (wrinkles) is extremely small.

FIG. 27 shows the XRD pattern of the precipitate in Comparative Example 3.
The XRD pattern showed periodic peaks of (001), (002), (003), (004), and (005), as in FIG. 24 of Example 2. The interplanar distance calculated from the (001) peak (intermolecular distance of the bilayer structure) was 3.5 nm.
Although not shown, it was confirmed that the film obtained from the precipitate of Comparative Example 3 did not exhibit super water repellency. Here again, the comparison between Example 2 and Comparative Example 3 suggests that the carbon of each alkyl chain of the fullerene derivative exhibits super water repellency at 20 or more.

  As described above, the supramolecular organization according to the present invention comprises a specific fullerene derivative. Such a specific fullerene derivative forms a bilayer structure in the supramolecular organization and functions as a nanostructure basic skeleton. As a result, the supramolecular organization exhibits super water repellency. The supramolecular organization according to the present invention can be used for various members and products that are required to be waterproof, anti-fogging, moisture-proof, anti-icing and snow-resistant. Furthermore, since the supramolecular structure according to the present invention has chemical resistance, acid / alkali resistance and heat resistance, it can be applied to any environment and any substrate. In addition, the supramolecular structure according to the present invention can be used as a high mechanical durability material having super water repellency and an optoelectronic material having super water repellency. Furthermore, the supramolecular organization of the present invention may be applied to MEMS / NEMS, microchannels, etc. that require low friction and non-wetting.

(A) Bimolecular film structure, (B) Flour-like fullerene structure and (C) Layered structure of supramolecular structure according to the present invention The figure which shows the flowchart which manufactures the supramolecular organization body by this invention A photograph showing the state of the solution immediately after heating in Example 1 and the state of the solution after aging SEM image and optical microscope image of the precipitate in Example 1 TEM image of precipitates in Example 1 Cryo-TEM image and Fourier transform pattern of precipitate in Example 1 XRD pattern of the precipitate in Example 1 The figure which shows the temperature dependence of the differential calorie | heat amount of the precipitate in Example 1. SEM image of the surface of the film on the Si substrate in Example 1 The figure which shows the mode of the water droplet of the film | membrane on the Si substrate in Example 1. The figure which shows the heat resistance of the film | membrane on the Si substrate in Example 1. The figure which shows the chemical resistance of the film | membrane on the Si substrate in Example 1. Another figure which shows the chemical resistance of the film | membrane on Si substrate in Example 1 The figure which shows the acid resistance of the film | membrane on the Si substrate in Example 1. The figure which shows the alkali resistance of the film | membrane on the Si substrate in Example 1. SEM image of the precipitate in Comparative Example 1 XRD pattern of precipitates in Comparative Example 1 The figure which shows the mode of the water droplet of the film | membrane on the Si substrate in the comparative example 1 AFM image of film surface on Si substrate in Comparative Example 2 The figure which shows the mode of the water droplet of the film | membrane on the quartz substrate in the comparative example 2 SEM image of the precipitate in Example 2 Another SEM image of the precipitate in Example 2 Another SEM image of the precipitate in Example 2 XRD pattern of precipitate in Example 2 The figure which shows the mode of the water droplet of the film | membrane on the Si substrate in Example 2. SEM image and optical microscope image of precipitate in Comparative Example 3 XRD pattern of precipitates in Comparative Example 3

Explanation of symbols

100 Bimolecular Structure 110 Fullerene Derivative 120 Flowery Fullerene Structure 130 Layered Structure 140 Base Material

Claims (6)

A fullerene structure in which fullerene derivatives having a bilayer structure are organized, the fullerene derivative comprising a fullerene moiety (A) represented by formula (1) and benzene bonded to the fullerene moiety (A) A ring, and first to third substituents R ₁ , R ₂ and R ₃ bonded to the 3, 4 and 5 positions of the benzene ring,

Here, in the formula (1), X is a hydrogen atom or a methyl group,
Each of the first and second substituents R ₁ , R ₂ is an alkyl chain comprising at least 20 carbon atoms;
Said third substituent R ₃ is either a hydrogen atom or an alkyl chain comprising at least 20 carbon atoms,
The alkyl chains of the _first to third substituents R ₁ , R ₂ and R ₃ are respectively alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ). Wherein n is an integer greater than or equal to 20,
A supramolecular organization characterized by having a flower- like shape and having the fullerene structure organized in layers. The supramolecular organization according to claim 1, wherein the fullerene bound to the fullerene moiety (A) is selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ , and C _84. Molecular organization. A method for producing a supramolecular organization according to claim 1 or 2,
A step of mixing a fullerene derivative and 1,4-dioxane, wherein the fullerene derivative comprises a fullerene moiety (A) represented by formula (1) and a benzene ring bonded to the fullerene moiety (A); And first to third substituents R ₁ , R ₂ and R ₃ bonded to the 3, 4 and 5 positions of the benzene ring,

Here, in the formula (1), X is a hydrogen atom or a methyl group, and each of the first and second substituents R ₁ and R ₂ is an alkyl chain containing at least 20 carbon atoms. And the third substituent R ₃ is either a hydrogen atom or an alkyl chain containing at least 20 carbon atoms, and the first to third substituents R ₁ , R ₂ And the alkyl chain of R ₃ is each selected from the group consisting of alkyl (C _n H _{2n + 1} ), alkoxyl (OC _n H _{2n + 1} ), and thioalkyl (SC _n H _{2n + 1} ), where n is 20 or more A step that is an integer of
Heating the mixture obtained by the mixing step;
Aging the mixture;
And a step of applying a solution containing a precipitate generated by the aging step. The method according to claim 3, wherein the fullerene binding to the fullerene moiety (A) is selected from the group consisting of C ₆₀ , C ₇₀ , C ₇₆ , and C ₈₄ .   5. The method according to claim 3, wherein the heating is performed in a temperature range of 60 ° C. to 70 ° C. for 1 to 2 hours. The method according to claim 3, wherein the aging is performed at room temperature for 12 to 24 hours.